Scorpionate (or trispyrazolylborate) ligands have seen much structural variation due to the relative ease of modifying their electronic and steric effects. Second-generation scorpionates were created by increasing the bulk in the 3-position of the pyrazole (pz) ring. A new class of third-generation scorpionates was obtained by modifying the remaining boron substituent. A series of thallium(I) and cobalt(II) complexes of the ferrocenyltris(3-R-pyrazolyl)borate ligand [FcTp; R = isopropyl (Pr) or tert-butyl (Bu)] have been synthesized in order to expand the range of redox-active third-generation scorpionates. These are [ferrocenyltris(3-tert-butylpyrazol-1-yl-κN)borato]thallium(I), [FeTl(CH)(CHBN)], [ferrocenyltris(3-isopropylpyrazol-1-yl-κN)borato]thallium(I), [FeTl(CH)(CHBN)], chlorido[ferrocenyltris(3-tert-butylpyrazol-1-yl-κN)borato]cobalt(II), [CoFe(CH)(CHBN)Cl], [ferrocenyltris(3-tert-butylpyrazol-1-yl-κN)borato]iodidocobalt(II) benzene disolvate, [CoFe(CH)(CHBN)I]·2CH, and [ferrocenyltris(3-isopropylpyrazol-1-yl-κN)borato]iodidocobalt(II), [CoFe(CH)(CHBN)I]. The structures demonstrate that the metal coordination site can easily be modified by using bulkier substituents at the pz 3-position.
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